CN116099379A - Screening vibrating diaphragm with piezoelectric ceramic array structure as supporting body and preparation method - Google Patents
Screening vibrating diaphragm with piezoelectric ceramic array structure as supporting body and preparation method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
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Abstract
The invention relates to a preparation method of a screening vibrating diaphragm with a piezoelectric ceramic array structure as a support. The preparation process comprises the steps of adopting a tape casting process to prepare Al 2 O 3 A membrane as a separation transition layer; al is bonded by a polymer binder 2 O 3 Compounding the base film with a thermoplastic mold; preparing a piezoelectric ceramic array structure by adopting a gel casting process, and demoulding at a proper temperature to obtain the piezoelectric array ceramic/Al 2 O 3 A composite green body; and (3) calcining the obtained composite green body in a high-temperature furnace, and carrying out high-pressure polarization to obtain the piezoelectric composite sieving vibrating membrane. Compared with the traditional asymmetric piezoelectric composite membrane, the composite membrane prepared by the inventionThe pore diameter of the combined vibration sieve membrane can be regulated and controlled in a narrow pore diameter gradient way at 1-1000nm so as to meet the high separation precision requirements of different separation systems; the permeation resistance is concentrated and distributed on the ultrathin separation layer, so that the permeation flux is higher; under the action of an electric field, the self-cleaning performance is further improved through the synergistic effect between the piezoelectric arrays.
Description
Technical Field
The invention relates to a preparation method of a screening vibrating diaphragm with a piezoelectric array structure as a support body, in particular to a controllable construction of the piezoelectric array structure.
Background
The membrane separation technology uses selective permeable membranes as separation media, and the components on the raw material side selectively permeate the membranes by applying a certain driving force on the two sides of the membranes so as to achieve the purpose of separation and purification. The ceramic membrane has the advantages of no phase change, low energy consumption, high efficiency, simple process and the like, and the ceramic membrane has the advantages of acid and alkali corrosion resistance, organic solvent resistance, high temperature resistance, high pressure resistance and the like, so that the ceramic membrane has a very wide application prospect. Membrane pollution is a common problem faced by membrane separation technology in the practical application process, and pollutants can be accumulated on the surface of a membrane or in a membrane pore canal to cause a membrane pollution phenomenon, so that not only is the membrane filtration flux seriously attenuated, but also the interception performance of separation substances of the membrane can be influenced, and the economy and reliability of the membrane separation process are directly influenced.
The porous piezoelectric ceramic membrane with self-cleaning performance is prepared, and in the membrane separation process, through applying alternating voltage excitation on two sides of the membrane, pollutants accumulated in the surface and pore channels of the membrane can be effectively removed, concentration polarization is relieved, and the porous piezoelectric ceramic membrane is proved to be in oil-water emulsion, protein purification and other systems. However, the piezoelectric ceramic membrane has low permeation separation efficiency, and it is difficult to improve permeation performance while improving anti-pollution performance.
At present, related reports for improving self-cleaning performance and permeability of piezoelectric ceramics mainly include Mao (J.Eur. Ceram. Soc.2020, 40:3632-3641) and the like, which prepare a PZT piezoelectric film with high flux and high piezoelectric performance through secondary sintering. To improve the separation precision of the PZT separation film, al is constructed on the surface of the piezoelectric film 2 O 3 The separation layer and the PZT piezoelectric micro-filtration membrane show higher normalized flux and interception effect in an oil-water separation system.
Disclosure of Invention
The invention aims to solve the technical problem that the piezoelectric ceramic separation membrane has low permeation efficiency. The invention aims at providing a preparation method of a piezoelectric array vibration screening membrane with a separation layer and a piezoelectric layer acting independently. The piezoelectric array vibration screening membrane prepared by the method has lower penetration resistance, higher separation efficiency and stronger piezoelectric response signal. The preparation method of the screening vibrating diaphragm with the piezoelectric ceramic array structure as the support combines the tape casting and gel casting processes, and prepares the piezoelectric ceramic array column by using the thermoplastic material as the template.
A sieving vibration membrane using piezoelectric ceramic array structure as support body comprises a selective separation layer, a base membrane and a support body, wherein the selective separation layer and the support body are respectively positioned at two sides of the base membrane, the base membrane is a porous ceramic sheet layer, the support body is a piezoelectric ceramic block array positioned at one side of the support body, the distance between piezoelectric ceramic blocks in the array is 0.1-5mm, and the projection area of the piezoelectric ceramic blocks on the selective separation layer is 0.5-5mm 2 。
The thickness of the basal membrane is 100-2000 mu m, the material is porous ceramic, and the aperture range is 0.01-5 mu m.
The thickness of the separation layer is 1-50 mu m, the material is porous ceramic, and the aperture range is 1-1000nm.
The piezoelectric ceramic material in the piezoelectric ceramic block is lead zirconate titanate (PZT), potassium sodium niobate (KNN), barium titanate (BaTiO) 3 ) One of them.
The preparation method of the screening vibrating membrane with the piezoelectric ceramic array structure as the support body comprises the following steps:
and 4, carrying out polarization treatment on the piezoelectric ceramic block array.
In the step 1, the base film and the mold are fixed by a polymer binder, wherein the polymer binder can be one of polyvinyl alcohol (PVA), polyethylene glycol (PEG) and polyvinylidene fluoride (PVDF).
In the step 2, the slurry contains piezoelectric ceramic powder, a dispersing agent and a crosslinking agent; the solid content of the slurry is 50-80wt%; the crosslinking reaction organic monomer is polyvinyl alcohol; the solvent is water; the cross-linking agent is 2, 5-dimethoxy dihydrofuran; the dispersing agent is N, N-bis (2-hydroxyethyl) glycine.
In the step 2, the weight ratio of the organic monomer to the cross-linking agent is 10-100: 1, the mass ratio of the dispersing agent to the piezoelectric ceramic powder is 1-5: 100.
the curing treatment is curing by crosslinking at 60-120 ℃ for 0.5-5 h.
The mold material can be one of polypropylene (PP), polyethylene (PE) and Polytetrafluoroethylene (PTFE), the demolding process refers to raising the temperature to 160-450 ℃, and the mold is automatically pyrolyzed into liquid or gas.
In the step 2, the sintering temperature is 1100-1500 ℃.
In step 2, the particles in the sol or film forming liquid may be Al 2 O 3 、ZrO 2 TiO 2 The coating time is controlled to be 30-300 s.
In the step 4, the polarization electric field intensity is 1-10 kV/mm; the polarization temperature is 60-140 ℃; the polarization time is 0.5-2 h.
The use of the sieving diaphragm described above in liquid filtration.
In the application process, the sieving vibrating diaphragm and the vibrating diaphragm are sealed in the assembly, the assembly further comprises a sealing unit and an outer tube, the sealing unit and the outer tube are arranged outside the base film and the support body, and the outer tube is arranged outside the sealing unit.
The sealing unit comprises a rubber gasket, a first fixing ring, a second fixing ring and an inner tube, wherein the rubber gasket is arranged at the lower end of the outer ring supporting body, the first fixing ring is arranged on the outer wall of the lower end of the inner tube, the second fixing ring is arranged below the rubber gasket, and a fastening mechanism is arranged between the second fixing ring and the first fixing ring.
The fastening mechanism comprises two symmetrically distributed thread grooves and fastening bolts, the two symmetrically distributed thread grooves and the fastening bolts are formed in the wall body of the first fixing ring, the fastening bolts are connected with the inner threads of the thread grooves, and the lower ends of the fastening bolts are rotationally connected with the second fixing ring.
The inner pipe is characterized in that an inner thread is arranged on the outer wall of the inner pipe, an outer thread matched with the inner thread is arranged on the inner wall of the outer pipe, and the inner thread is in threaded connection with the outer thread.
Advantageous effects
(1) The porous piezoelectric support body is changed into piezoelectric array ceramic, so that the permeation resistance of the piezoelectric film can be greatly reduced, and the permeation flux can be improved;
(2) The piezoelectric array ceramics can form gaps among each other, the gaps form a rapid outflow channel of penetrating fluid, and meanwhile, the piezoelectric array ceramics can be used as a supporting body, so that the mechanical supporting force of the separation layer in the running process is maintained;
(3) Meanwhile, through the synergistic effect among the piezoelectric array ceramics, the in-situ ultrasonic signal is further amplified, and the self-cleaning performance is improved. Therefore, the preparation of the piezoelectric array screening vibrating diaphragm has great significance;
(4) The size parameters of the prepared piezoelectric array column can be adjusted according to the die;
(5) The piezoelectric ceramic array unit provides strength for the composite sieving membrane;
(6) According to an actual separation system, a narrow-aperture separation membrane can be constructed on the base membrane, so that the separation precision is improved;
(7) Compare traditional with the sealing washer setting on the lateral wall of base film, can make when using the base film give the effort on the support body horizontal direction of base film lower extreme and then cause the support body to break easily, with the setting that the base film breaks away from, solid fixed ring in the sealed unit in this application is first, solid fixed ring second and rubber gasket give the base film and support body be the ascending effort of vertical direction, has not only increased the leakproofness that the piezofilm used, has still increased the compactness between support body and the base film to the stability in use of filter membrane has been increased, has increased the result of use to the piezofilm.
Drawings
Fig. 1: preparing a simplified diagram of the piezoelectric array composite screening membrane;
fig. 2: piezoelectric signals of the piezoelectric composite screening membrane detected by the hydrophone;
fig. 3: a pure water permeability graph of the piezoelectric array composite sieving membrane along with pressure change;
fig. 4: a cross-section front view structural schematic diagram of the base film, the support body, the outer tube, the rubber gasket and the sealing unit;
fig. 5: the base film, the supporting body, the rubber gasket and the sealing unit are structurally schematic;
fig. 6: the inner pipe and the outer pipe are connected with an external structure schematic diagram;
in the figure: 1 a base film; 2. a support body; 3. a sealing unit; 31. a rubber gasket; 32. a first fixed ring; 33. a second fixing ring; 34. an inner tube; 35. a fastening mechanism; 351. a thread groove; 352. a fastening bolt; 4. an outer tube; 5. an internal thread; 6. and (5) external threads.
Detailed Description
The preparation process of the sieving vibrating membrane is detailed as follows:
the method comprises the following steps:
1) Al having a pore diameter of 1 μm and a thickness of 500 μm was prepared by a casting process 2 O 3 Base film of Al 2 O 3 The base film is coated with a polymer binder, and Al is added under the action of the combination force 2 O 3 Compounding the base film with thermoplastic molds of different shapes;
2) The piezoelectric ceramic powder is used as a raw material, and the addition amount of an organic monomer, a dispersing agent and a cross-linking agent is controlled to obtain ceramic slurry with good dispersibility and high solid content;
3) Injecting piezoelectric ceramic slurry into the Al 2 O 3 In the composite mould, the adding amount of the slurry is regulated and controlled, and the slurry is crosslinked and solidified at a certain temperature, dried and formed;
4) Demoulding the dried piezoelectric green body, the mould and the base film to obtain a piezoelectric ceramic/Al 2O3 composite green body, and controlling the temperature to sinter and compact internal grains of the piezoelectric array ceramic;
5) Placing the sintered piezoelectric ceramic composite membrane into a sol/membrane preparation solution which is uniformly dispersed, and drying and calcining to prepare a high-precision sieving membrane;
6) And placing the high-precision piezoelectric composite sieving membrane in insulating oil, and controlling polarization conditions to endow the high-precision piezoelectric composite sieving membrane with piezoelectric performance.
The thermoplastic die material can be one of polypropylene (PP), polyethylene (PE) and Polytetrafluoroethylene (PTFE); the mold shape may be one of (a) a single cylindrical shape having a diameter of 3cm, (b) an array cylindrical shape having a diameter of 1mm and a pitch of 2mm, (c) an array cylindrical shape having a diameter of 2mm and a pitch of 2 mm.
The polymer binder may be one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), and polyvinylidene fluoride (PVDF).
The piezoelectric ceramic powder can be lead zirconate titanate (PZT), potassium sodium niobate (KNN) or barium titanate (BaTiO) 3 ) One of the following; the solid content of the piezoelectric ceramic slurry is 50-80wt%.
The crosslinking reaction organic monomer is polyvinyl alcohol; the solvent is water; the cross-linking agent is 2, 5-dimethoxy dihydrofuran; the dispersing agent is N, N-bis (2-hydroxyethyl) glycine; the mixing mode is magnetic stirring.
The weight ratio of the organic monomer to the cross-linking agent is 10-100: 1, the mass ratio of the dispersing agent to the piezoelectric powder is 1-5: 100; crosslinking and curing means crosslinking for 0.5 to 5 hours at the temperature of between 60 and 120 ℃; the drying and forming are that the materials are naturally dried for 12 to 48 hours and then are dried for 1 to 24 hours at the temperature of 70 to 110 ℃;
the demolding process is to raise the temperature to 160-450 deg.c and to make the mold pyrolyze into liquid or gas.
The piezoelectric ceramic/Al 2 O 3 The calcination temperature of the composite green compact is 1100-1500 ℃, and the polarized electric field strength is 1-10 kV/mm; the polarization temperature is 60-140 ℃; the polarization time is 0.5-2 h.
The particles of the sol/film-forming liquid can be Al 2 O 3 、ZrO 2 TiO 2 The coating time is controlled to be 30-300 s.
Example 1 preparation method of screening vibration film with KNN piezoelectric ceramic array structure as support
Pore diameter is adjustedAl of 1 μm 2 O 3 The base film is compounded with polypropylene molds with different shapes through a high molecular binder PVA. The piezoelectric array ceramic support is prepared by taking KNN powder as a raw material, taking polyvinyl alcohol as an organic monomer, taking 2, 5-dimethoxy dihydrofuran as a cross-linking agent and taking N, N-bis (2-hydroxyethyl) glycine as a dispersing agent through a gel casting process.
Polyvinyl alcohol as an organic monomer was dissolved in HNO at ph=0.5 3 Preparing PVA premix with 5wt%, adding 100g KNN powder (average particle size 500 nm) into 30g premix, mixing 3g N, N-bis (2-hydroxyethyl) glycine, adding 0.06g 2, 5-dimethoxy dihydrofuran (organic monomer and cross-linking agent with mass ratio of 25:1) and 0.006g N-butanol, mixing again, and injecting Al 2 O 3 The polypropylene array mould (b) and (c) of the base film composite are sealed (the mould shape can be (b) array cylinder shape with the diameter of 1mm and the interval of 2mm, and (c) array cylinder shape with the diameter of 2mm and the interval of 2 mm). Putting into an oven at 80 ℃ for 60min, taking out, naturally airing for 12h, putting into an oven at 110 ℃ for 8h, taking out, naturally airing, and putting into an oven at 200 ℃ for demoulding. Obtaining KNN/Al 2 O 3 And (5) compounding the array green body. And then placing the mixture in a high-temperature furnace at 1100 ℃ for calcination to obtain the piezoelectric array vibration screening composite membrane. Polarizing the composite membrane in mineral oil at 130 ℃, wherein the polarizing voltage is 4kV/mm, the polarizing time is 30min, and the piezoelectric response signals detected by the piezoelectric array composite membrane under the excitation of 20V alternating current are respectively 50mV and 44mV, as shown in figure 2; permeability of 20m respectively 3 ·m -2 ·h -1 ·bar -1 And 18m 3 ·m -2 ·h -1 ·bar -1 As shown in fig. 3.
Example 2 preparation method of sieving composite Membrane Using KNN piezoelectric porous Structure as support
The piezoelectric ceramic paste obtained in example 1 was poured into Al 2 O 3 The polypropylene mold (a) (the shape of the mold can be (a) a single cylinder with the diameter of 3 cm) compounded by the base film, and the crosslinking, drying and demolding processes are the same as those of the embodiment 1, so as to obtain KNN/Al 2 O 3 And (3) calcining the composite green body in a high-temperature furnace at 1000 ℃ to obtain the piezoelectric porous vibration screening membrane. The polarization conditions were the same as those of example 1, the pressureThe piezoelectric response signal of the electro-porous composite membrane detected under the excitation of 20V alternating voltage is 20mV, and as shown in FIG. 2, the permeability is 165 L.m -2 ·h -1 ·bar -1 As shown in fig. 3.
EXAMPLE 3KNN/Al 2 O 3 High-precision aperture gradient regulation and control method of piezoelectric composite membrane
KNN/Al obtained in example 1 and example 2 2 O 3 The piezoelectric composite film is arranged in Al 2 O 3 In the membrane preparation liquid, the coating time is 100s, and the piezoelectric composite micro-filtration membrane is obtained through high-temperature calcination; to further improve the separation accuracy, the microfiltration membrane is placed in Al 2 O 3 Coating in sol for 100s, and calcining to obtain the piezoelectric composite ultrafiltration membrane. The micro-filtration membrane/ultra-filtration membrane is placed in insulating oil for high-voltage polarization under the same polarization condition as in example 1, the piezoelectric response signals detected by the piezoelectric array composite membrane under the excitation of 20V alternating current are respectively 21mV and 18mV, and the permeability is respectively 3.2m 3 ·m -2 ·h -1 ·bar -1 And 0.8m 3 ·m -2 ·h -1 ·bar -1 The average pore diameters are about 100nm and about 10nm, respectively.
Example 4 BaTiO 3 Preparation method of screening vibrating membrane with piezoelectric ceramic array structure as supporting body
Al with a pore diameter of 1 μm 2 O 3 The base film is compounded with polypropylene molds with different shapes through a high molecular binder PVA. By BaTiO 3 The powder is used as raw material, polyvinyl alcohol is used as organic monomer, 2, 5-dimethoxy dihydrofuran is used as cross-linking agent, N, N-bis (2-hydroxyethyl) glycine is used as dispersing agent, and the piezoelectric array ceramic support is prepared through gel casting process.
Polyvinyl alcohol as an organic monomer was dissolved in HNO at ph=0.5 3 A PVA premix of 5wt% was prepared, and 100g of BaTiO was added to 30g of the premix 3 3g of N, N-bis (2-hydroxyethyl) glycine is evenly mixed, then 0.06g of 2, 5-dimethoxy dihydrofuran (the mass ratio of organic monomer to cross-linking agent is 25:1) and 0.006g of N-butanol are added for mixing again, and Al is injected 2 O 3 Polypropylene array die composited by base film(b) And (c) back sealing (the mold shape may be (b) 1mm diameter, 2mm pitch array cylinder, (c) 2mm diameter, 2mm pitch array cylinder). Putting into an oven at 80 ℃ for 60min, taking out, naturally airing for 12h, putting into an oven at 110 ℃ for 8h, taking out, naturally airing, and putting into an oven at 200 ℃ for demoulding. Obtaining BaTiO 3 /Al 2 O 3 And (5) compounding the array green body. And then placing the mixture in a high-temperature furnace at 1400 ℃ for calcination to obtain the piezoelectric array vibration screening composite membrane. Polarizing the composite film in 120 deg.c mineral oil with polarizing voltage of 3kV/mm and polarizing time of 60min, piezoelectric response signals of 150mV and 139mV detected with 20V AC excitation and permeabilities of 2.2m 3 ·m -2 ·h -1 ·bar -1 And 1.8m 3 ·m -2 ·h -1 ·bar -1 。
The application of the screening vibrating diaphragm in liquid filtration further comprises a sealing unit 3 and an outer tube 4 which are arranged outside the base film 1 and the support body 2, the outer tube 4 is arranged outside the sealing unit 3, and the sealing unit 3 not only increases the sealing performance of the piezoelectric film, but also increases the tightness between the support body 2 and the base film 1.
The sealing unit 3 comprises a rubber gasket 31, a first fixing ring 32, a second fixing ring 33 and an inner tube 34, wherein the rubber gasket 31 is arranged at the lower end of the outer ring support body 2, the first fixing ring 32 is arranged on the outer wall of the lower end of the inner tube 34, the second fixing ring 33 is arranged below the rubber gasket 31, and a fastening mechanism 35 is arranged between the second fixing ring 33 and the first fixing ring 32.
The fastening mechanism 35 comprises two symmetrically distributed thread grooves 351 and fastening bolts 352 which are formed in the wall body of the first fixing ring 32, the fastening bolts 352 are connected with the lower ends of the thread grooves 351 in a threaded mode, the fastening bolts 352 are connected with the second fixing ring 33 in a rotating mode, when the fastening mechanism is used, the fastening mechanism 352 is rotated firstly, then the second fixing ring 33 is made to be close to the first fixing ring 32 under the action of the thread grooves 351, acting force on the vertical direction of the support body 2 is applied, the fastening performance between the support body 2 and the base film 1 is improved, the fastening performance between the rubber gasket 31 and the lower end of the outer ring support body 2 is improved, and the sealing effect is achieved by matching with the arrangement of the inner pipe 34 and the outer pipe 4. The fastening bolt 352 is used for enabling the outer ring support body 2 to be stressed in the vertical direction, so that the problem of support body damage or service life caused by the fact that the outer ring support body 2 is stressed in the horizontal direction due to the fact that a sealing ring is sleeved on the side portion of the base film 1 by adopting a conventional method is solved.
The outer wall of the inner tube 34 is provided with an inner thread 5, the inner wall of the outer tube 4 is provided with an outer thread 6 matched with the inner thread 5, the inner thread 5 is in threaded connection with the outer thread 6, and the inner tube 34 can be directly rotated into the outer tube 4 through the arrangement of the inner thread 5 and the outer thread 6, so that the installation and fixation work of the inner tube 34 and a voltage membrane is completed.
Claims (10)
1. A screening vibration film taking a piezoelectric ceramic array structure as a supporting body is characterized by comprising a selective separation layer, a base film (1) and a supporting body (2), wherein the selective separation layer and the supporting body (2) are respectively positioned at two sides of the base film (1), the base film (1) is a porous ceramic sheet layer, the supporting body (2) is a piezoelectric ceramic block array positioned at one side of the supporting body (2), the distance between the piezoelectric ceramic blocks in the array is 0.1-5mm, and the projection area of the piezoelectric ceramic blocks on the selective separation layer is 0.5-5mm 2 。
2. The screening vibration film using the piezoelectric ceramic array structure as a support body according to claim 1, wherein the thickness of the base film is 100-2000 μm, the material is porous ceramic, and the pore diameter range is 0.01-5 μm; the thickness of the separation layer is 1-50 mu m, the material is porous ceramic, and the aperture range is 1-1000nm.
3. The sieving membrane with the piezoelectric ceramic array structure as a support body according to claim 1, wherein the piezoelectric ceramic material in the piezoelectric ceramic block is lead zirconate titanate (PZT), potassium sodium niobate (KNN), barium titanate (BaTiO) 3 ) One of them.
4. The method for preparing the sieving vibrating membrane with the piezoelectric ceramic array structure as a support body as claimed in claim 1, comprising the following steps:
step 1, one side of a base film is fixed with a die, and the die is provided with an opening matched with the array shape of a piezoelectric ceramic block;
step 2, adding slurry containing piezoelectric ceramic powder into the open pores, demoulding after curing treatment, and sintering to obtain a piezoelectric ceramic block array;
step 3, sol or film-making liquid is applied to the other side of the base film, and a selective separation layer is obtained after sintering;
and 4, carrying out polarization treatment on the piezoelectric ceramic block array.
5. The method of claim 4, wherein in the step 1, the base film and the mold are fixed by a polymer binder, and the polymer binder may be one of polyvinyl alcohol (PVA), polyethylene glycol (PEG) and polyvinylidene fluoride (PVDF).
6. The method for preparing a sieving vibrating membrane with a piezoelectric ceramic array structure as a support according to claim 4, wherein in the step 2, the slurry contains piezoelectric ceramic powder, a dispersing agent and a crosslinking agent; the solid content of the slurry is 50-80wt%; the crosslinking reaction organic monomer is polyvinyl alcohol; the solvent is water; the cross-linking agent is 2, 5-dimethoxy dihydrofuran; the dispersing agent is N, N-bis (2-hydroxyethyl) glycine;
in the step 2, the weight ratio of the organic monomer to the cross-linking agent is 10-100: 1, the mass ratio of the dispersing agent to the piezoelectric ceramic powder is 1-5: 100.
7. the method for preparing a sieving diaphragm with a piezoelectric ceramic array structure as a support according to claim 4, wherein the curing treatment is curing by crosslinking at 60-120 ℃ for 0.5-5 h; the die material can be one of polypropylene (PP), polyethylene (PE) and Polytetrafluoroethylene (PTFE), the demolding process refers to the process of raising the temperature to 160-450 ℃, and the die is automatically pyrolyzed into liquid or gas;
in the step 2, the sintering temperature is 1100-1500 ℃;
in step 2, theThe particles in the sol or film-forming liquid can be Al 2 O 3 、ZrO 2 TiO 2 The coating time is controlled to be 30-300 s.
8. The method for preparing a sieving diaphragm with a piezoelectric ceramic array structure as a support according to claim 4, wherein in step 4, the polarized electric field strength is 1-10 kV/mm; the polarization temperature is 60-140 ℃; the polarization time is 0.5-2 h.
9. Use of a sieving diaphragm with a piezoceramic array structure as support according to claim 1 for liquid filtration.
10. Use according to claim 9, wherein the sieving diaphragm is sealed in a module comprising a sealing unit (3) and an outer tube (4) arranged outside the base membrane (1) and the support body (2), the outer tube (4) being arranged outside the sealing unit (3);
the sealing unit (3) comprises a rubber gasket (31), a first fixing ring (32), a second fixing ring (33) and an inner tube (34),
the rubber gasket (31) is arranged at the lower end of the outer ring support body (2), the first fixing ring (32) is arranged on the outer wall of the lower end of the inner tube (34), the second fixing ring (33) is arranged below the rubber gasket (31), and a fastening mechanism (35) is arranged between the second fixing ring and the first fixing ring (32);
the fastening mechanism (35) comprises two symmetrically distributed thread grooves (351) which are arranged on the wall body of the first fixing ring (32)
The fastening bolt (352) is connected with the fastening bolt (352) through threads in the threaded groove (351), and the lower end of the fastening bolt (352) is rotationally connected with the second fixing ring (33);
an inner thread (5) is arranged on the outer wall of the inner tube (34), an outer thread (6) matched with the inner thread (5) is arranged on the inner wall of the outer tube (4), and the inner thread (5) is in threaded connection with the outer thread (6).
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